Water-insoluble monoazo dyestufs

ABSTRACT

Water-insoluble monoazo dyestuffs of the formula   IN WHICH A represents the radical of a diazo component, B represents a paraphenylene residue that may be substituted, R1 represents an alkyl group that may be substituted by groups other than benzoyloxy groups and R2 represents a residue of the formula -alkylene-O-COR3, in which R3 represents a benzene residue free from hydroxyl or carbalkoxy groups, a phenalkyl group, a styryl group, a five-membered heterocyclic residue or a nitrogen-free, six-membered heterocyclic residue, are useful for dyeing or printing polyester fibers in orange to blue tints fast to light and sublimation.

United States Patent Peter et a].

[m 3,821,194 1 June 28, 1974 I WATER-INSOLUBLE MONOAZO DYESTUFS [75] Inventors: Richard Peter, Basel; Hans-Joerg Angliker, Riehen; Klaus Artz, Muttenz, all of Switzerland [30] Foreign Application Priority Data Dec. 27, 1966 Switzerland 18616/66 [52] US. Cl 260/207, 260/152, 260/158, 26O/207.l, 260/332.2 C, 260/347.4, 8/41 C [51] Int. Cl. CO9b 29/08, CO9b 29/36 [58] Field of Search 260/152, 158, 207, 207.1

[56] References Cited UNITED STATES PATENTS 2,249,749 7/1941 Dickey et a1 260/152 2,323,314 7/1943 Dickey et a1 260/207.1 2,373,700 4/1945 McNally et a1. 260/207.1 3,445,454 5/1969 Fishwick ct a1 260/207 3,533,722 10/1970 Wegmuller 8/26 3,707,533 12/1972 Pohl 260/207 FOREIGN PATENTS OR APPLICATIONS 852,396 10/1960 Great Britain 260/207.1 1,461,855 11/1966 France 260/207.1

11/1962 GreatBritain ..260/207.l 2/1964 France ..260/158 Primary ExaminerLorraine A. Weinberger Assistant Examiner-C. F. Warren Attorney, Agent, or Firm-Joseph G. Kolodny; Stanley Marcus; Edward McC. Roberts [57] ABSTRACT Water-insoluble monoazo dyestuffs of the formula R1 AN=NBN/ in which A represents the radical of a diaz'o component, B represents a paraphenylene residue that may be substituted, R represents an alkyl group that may be substituted by groups other than benzoyloxy groups and R represents a residue of the formula a1kylene-O-COR in which R represents a benzene residue free from hydroxyl or carbalkoxy groups, a phenalkyl group, a styryl group, a five-membered heterocyclic residue or a nitrogen-free, six-membered heterocyclic residue, are useful for dyeing or printing polyester fibers in orange to blue tints fast to light and sublimation.

7 Claims, No Drawings 1 WATER-INSOLUBLE MONOAZO DYESTUFS The present invention provides, as new compounds, water-insoluble azo dyestuffs of the general formula in which A represents the residue of a diazo component, B represents a para-phenylene residue that may be substituted, R, represents an alkyl group that may be substituted by groups other than benzoyloxy groups and R represents a residue of the formula alkyleneOCOR in which R represents a benzene residue free from hydroxyl r carbalkoxy groups, a phenalkyl group, a 'styryl group, a five-membered heterocyclic residue or a nitrogen-free six-membered heterocyclic residue.

The invention also provides a process for the manufacture of water-insoluble azo dyestuffs of the above general formula, which comprises: (a) coupling a diazotized amine with an amine of the formula or (b) monoacylating or diacylating an azo dyestuff of the formula Rs V in which A and B have the meanings given above, R represents an alkyl group that may be substituted and R represents a hydroxyalkyl group, with a halide or an anhydride of a five-membered heterocyclic carboxylic acid, a six-membered, nitrogen-free heterocyclic carboxylic acid, a cinnamic acid or a phenylalkanecarboxylic acid acid, and/or monoacylating an azo dyestuff of the above formula (ll) with a benzoic acid halide or anhydride which is free from hydroxyl and carb- I alkoxy groups.

Preferred diazo components are aminobenzenes of the formula 2 nitrobenzene, l-amino-4-cyanobenzene, 1-amino-2,5- dicyanobenzene, l-amino-4-methylsulphonylbenzene, l-amino-4-carbalkoxybenzene, 1 -amino-2 ,4- dichlorobenzene, l-amino-2,4-dibromobenzene, 1- amino-2-methyl-4-chlorobenzene, l-amino-2- trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4- chlorobenzene, l -amino-2-carbomethoxy-4- chlorobenzene, l-amino-2-carbomethoxy-4- nitrobenzene, l-amino-2-chloro-4-cyanobenzene, l-

| alkylene-Xi in which X, represents a hydrogen atom or an alkoxy, cyanoalkoxy, phenyl or cyano group or a hydroxyl group acylated by the residue of an aliphatic carboxylic acid, cinnamic acid or phenylalkanoic acid, the residue of a five-membered heterocyclic carboxylic acid or the residue of a six-membered, nitrogen-free heterocyclic carboxylic acid, X represents a residue of the formula -OCOR in which R, has the meaning given above, and in which Y, represents a hydrogen or a halogen atom or an alkyl, alkoxy, aryloxy or acylamino group and Z, represents a hydrogen atom or an alkyl or alkoxy group.

Coupling components which are of special interest are those of the formula in which Y,, Z, and X have the meanings given above.

The following amines may be mentioned as exambenzyl-N-B-benzoyloxyethylaniline, N-B-cyanoethyl- N-B-benzoyloxyethyl-meta-toluidine,N-B-

acetoxyethyl-N-B-benzoyloxyethyl-meta-toluidine, [N-B-acetoxyethyl-N-B-benzoyloxyethyl]-amino-3- acetylaminobenzene, l-[ N-B-acetoxyethyl-N-B- benzoyloxyethyl l-amino-2-methoxy-5- acetylaminobenzene, N-B-cyanoethyl-N-B- phenacetoxyethylaniline, N-B-cyanoethyl-N-B-cinnaomoyloxyethylaniline, N-ethyl-N-B-(a-furoyhoxyethylaniline, N-B-cyanoethyl-N-B-(a-furoyl oxyethylaniline, N-bis-,B-[(a-furoyl)-oxyethyl]-aniline, N-B-cyanoethyl-N-B-(a-tetrahydrofuroyl)- oxyethylaniline, N-bis-[B-(a-tetrahydrofuroyl)- oxyethyl1-aniline, N-bis-[,B-(a-tetrahydrofuroyl)-oxyethyl]-meta-toluidine, N-B-acetoxyethyl-N-B-(athienoyl)-oxyethylaniline, N-B-cyanoethyl-N-B-(ozthienoyl)-oxyethylaniline, N-bis-[B-(a-thienoyD- oxyethyl]-aniline and N-B-benzoyloxyethyl-N-B- tetrahydrofuroyloxyethylaniline.

It is also possible to use a mixture of different coupling components and, in many cases, the dyestuffs obtained display better affinity and building-up properties than dyestuffs obtained with a single coupling component.

Diazotization of the above-mentioned diazo components may be carried out by methods known per se, for example, with a mineral acid, particularly hydrochloric acid, and sodium nitrite, or, for example, with a solution of nitrosyl-sulphuric acid in concentrated sulphuric acid.

Coupling may also be carried out by a known method, for example, in a neutral to acid medium, if necessary, in the presence of sodium acetate or a similar buffer which influences the rate of coupling, or a catalyst, for example, pyridine or a salt thereof.

After coupling, the dyestuffs formed can easily be separated from the coupling mixture, for example, by filtration, because they are virtually insoluble in water.

In process (b) of the invention the starting materials used are advantageously azo dyestuffs of the formula I alkylene-Xa in which Y, Z, Y, and 2, have the meanings given above and X, represents a hydrogen atom or a hydroxy, alkoxy cyano or carbalkoxy group.

The starting material is monoacylated or diacylated either with a halide or ananhydride of a fiv'e-membered heterocyclic carboxylic acid, a six-membered, nitrogen-free heterocyclic carboxylic acid, a phenylalkanecarboxylic acid or a cinnamic acid, or monoacylated with a benzoic acid halide or anhydride and, if

necessary, monoacylated with a chloride or anhydride of one of the above-mentioned heterocyclic carboxylic acids.

It is expedient to carry out acylation in an inert organic solvent, for example, pyridine, benzene, dioxane, isopropylether, ethyl acetate or dimethylformamide. When manufacturing compounds acylated with a single acylating agent, it is possible to use a large excess of the acylating agent instead of a solvent.

The new dyestuffs are eminently suitable for dyeing and printing materials, especially fibres and fabrics, made, for example, from cellulose triacetate and polyamides, but particularly aromatic polyesters. They produce on these materials strong dyeings possessing very good properties of fastness, especially very good fastness to light, sublimation and rubbing. The dyestuffs are also suitable for materials to be subjected to the permanent press process, 'for example, the Koratron process. Dyeings thus treated display very good properties of wet fastness and very good fastness to heat. The new dyestuffs are also eminently suitable for textured polyester yarn. In contrast to other dyestuffs, they produce dyeings which are free from streakiness.

For dyeing, the new dyestuffs are advantageously used in a finely divided form, and dyeing is carried out in the presence of a dispersing agent, for example, soap, sulphite cellulose waste liquor or a synthetic detergent, or a combination of different wetting and dispersing agents. Prior to dyeing, it is generallyadvantageous to convert the dyestuff into a dyeing preparation which contains a dispersing agent and the dyestuff in a form such that a fine dispersion is obtained when the preparation is diluted with water. Such dyestuff preparations may be obtained in known manner, for example, by reprecipitating the dyestuff from sulphuric acid and grinding the suspension so obtained with sulphite cellulose waste liquor. If necessary, they may also be obtained by grinding the dyestuff in a highly efficient grinding device in the dry or wet state in the presence or absence of a dispersing agent.

To obtain stronger dyeings on polyethylene terephthalate fibres it is generally advantageous to add a swelling agent to the dyebath, or more especially to carry out the dyeing process under superatmospheric pressure at a temperature above C, for example, at C. Suitable swelling agents are aromatic carboxylic acids, for example, benzoic acid and salicyclic acid; phenols, for example, orthoor para-hydroxydiphenyl; aromatic halogenated compounds, for example, chlorobenzene, ortho-dichlorobenzene and trichlorobenzene; and phenylmethylcarbinol or diphenyl. When carrying out the dyeing process under superatmospheric pressure it is generally advantageous to render the dyebath slightly acidic, for example, by the addition of a weak acid, for example, acetic acid.

By virtue of their fastness to alkali, the new dyestuffs are specially suitable for application by the so-called thermofixation process in which the material to be dyed is impregnated at a temperature not exceeding 60C with an aqueous dispersion of the dyestuff which advantageously contains 1 to 50- percent of urea and a thickening agent, especially sodium alginate, and then squeezed in the usual manner. The impregnated material is advantageously squeezed so as to retain 50 to 100 percent of its dry weight of dye-liquor.

To fix the dyestuff, the material so impregnated is heated to a temperature above 100C, for example, to

a temperature between 180 and 220C, advantageously after drying, for example, in a current of warm air.

The aforementioned thermofixation process is specially suitable for the dyeing of union fabrics made 5 weight. from polyester fibres and cellulosic fibres, especially cotton. In this case, in addition to the dyestuffs of the EXAMPLE 1 invention, the padding liquor contains dyestuffs suit- 1.63 Parts of 2-cyano-4-nitroaniline are added in porable for dyeing cotton, especially vat dyestuffs, or reactions to parts of monohydrate in which 0.7 part of tive dyestuffs, that is to say, dyestuffs capable of being l0 sodium nitrite has been dissolved. After some time, this fixed on the cellulosic fibre with formation of a chemidiazo component is discharged on to 100 parts of ice, cal bond, for example, dyestuffs which contain a chlothe excess of nitrite is destroyed, and a solution of 3 rotriazine or chlorodiazine residue. [n the latter case, parts of N-B-cyanoethyl-N43-benzoyloxyethylaniline in. it is generally advantageous to add an agent capable of 75 parts of glacial acetic acid is added. After some binding acid to the padding liquor, for example, an al- 15 time, the batch is buffered at a temperature not exceedkali metal carbonate, an alkali metal phosphate, an aling 10C with a 30 percent sodium hydroxide solution, kali metal borate or an alkali metal perborate, or mixwhich process completely precipitates the dyestuff. tures thereof. When using vat dyestuffs, the padded The dyestuff so obtained dyes polyester fibres red fabric must be treated after the heat treatment with an shades possessing excellent fastness to light and subliaqueous alkaline solution of one of the reducing agents mation. commonly used in vat dyeing. By virtue of the fact that The following table lists components for further dyethe dyestuffs of the invention reserve well on wool, they stuffs. The dyestuffs may be obtained by diazotizing the are eminently suitable for dyeing union fabrics made diazo components shown in Column 1 and then coufrom polyester fibre and wool. pling the diazo compound with the coupling compo- The dyeings obtained are advantageously subjected nents shown in Column ll. The shades obtained on to an after-treatment, for example, by heating with an polyester fibres are indicated in Column Ill. aqueous solution of a non-ionic detergent. I H m The dyestuffs may also be a plied b rinting processes. In this method of applicgtion a griiiting paste is 3352555, ;Z f;1?ff5" Orange used which contains, for example, in addition to the gg'ggf' usual printing ad uvants, for example, thickening and 3--. 2-casfifipl--nltrocigrligiirdgggyggfiifmg fif y wettmg agents, the finely divided dyestuff, If necessary, 4 "do Phenylac'etic aeid ester of N-fl- Red. in admixture with one of the above-mentioned cotton cyamethyl'Nmxyethylmmne' I II III 5 2,6-dichloro4-nitroaniline C2H4CN Orange.

C2H4OCOCH=CHCsH5 6 2-chloro-4-nitroaniline S Ruby.

-N C.H.OCO C CH] H ylH 2 7 2-eyano-4-nitroaniline C2H4-ON 0 Red.

ON/ s i l-0cm \C2H4O-CC/ \C/ I iiH :H

8 2-ch1oro-4-nitroaniline C2H4-CN Orange-red.

o2H4-0o-c c-cfiocm g (H3HCH 9 2-cyano-4-nitroaniline C2H4CN Red.

' C2H4-OCC ,\CH2 0 o ly-(i112 10 2-chloro-4nitroani1ine Same as above Orange-red.

11 2,4-dinitro-6-ehloroaniline O S 0 Navy blue.

OCHa II .II..

I (CzH4-O-C--C c-oocm dyestuffs, if necessary, together with urea and/or an agent capable of binding acid.

The following Examples illustrate the invention. Unless otherwise stated, the parts and percentages are by Continued I II III 12 AmynnM-nlbrnanfllnc I I A V CzIh-CN' I Red. 7

C2H4O(-C CH Ha H H CH-CH 13.. ..d0 C2H4-CN Red.

c2m 0-c c OH OCH; H CH--CH 14 2,6'dich1oro-4-nitroani1ine 02H4-CN Orange 15 2-ch1oro4-nitroani1ine. -16. 4-nitroani1ine 17 2-cyano-4-nitroaniline .d

18 2-cyano4-n1troan1line CH4-CN CH Red.

19 ..d0 CgHr-CN Red- O CH:

CzHaQ C O 20 ..d0 CQHICN Red- CzHcO C O O 02H:

21 2-chloro-4-nitroanillne CzHCN Orange- Qfl 22 (300C113 /CzH CN Scarlet.

0 H I Q N- N 2 O 2 C2H4O C O-% fiH HCCH 23 N CzH|CN Red.

C NH OzN- 2 can-0 coc s 111 S HC--CH 24 /N Same as above Orange.

C H o /.CNH2

25 Q..." TN ...do Violet.

OZNL J NH2 s v 26 2-cyano-4-n1troaniline CzH4CN Red.

EXAMPLE 2 EXAMPLE 3 A dyestuff which dyes polyester fibres red shades possessing excellent fastness to light and sublimation may be obtained by replacing the 3 parts of furan-2- carboxylic acid chloride given in Example 2 with 3.5 parts of thiophene-Z-carboxylic acid chloride.

EXAMPLE 4 A dyestuff which dyes polyester fibres red shades possessing excellent fastness to light and sublimation may be obtained by replacing the 3 parts of furan-2- carboxylic acid chloride given in Example 2 with 3 parts of tetrahydrofuran-2-carboxylic acid chloride.

EXAMPLE 5 A dyestuff which dyes polyester fibres red shades possessing excellent fastness to light and sublimation may be obtained by replacing the 3 parts of furan-2- carboxylic acid chloride given in Example 2 with 4.5 parts of thiophene-Z-carboxylic acid chloride-5- carboxylic acid methylester.

3 5 Dyeing Procedure 1 Part of the dyestuff obtained in the manner described in the first paragraph of Example l is ground wet with 2 parts of a 50 percent aqueous solution of the sodium salt of dinaphthylmethane-2,2-disulphonic acid and the batch is dried.

The dyestuff preparation so obtained is mixed with parts of a 10 percent aqueous solution of a condensation product obtained from octadecyl alcohol and 20 mols of ethylene oxide, and then 4 parts of a 40 percent acetic acid solution are added. A dyebath of 4,000

parts is prepared therefrom by dilution with water.

100 Parts of a cleansed polyester fibre material are entered into this bath at C, the temperature is raised to 120 to 130C within half an hour and dyeing is carried out for 1 hour at that temperature in a closed vessel. The material is then well rinsed. A strong red dyeing possessing excellent fastness to light and sublimation is obtained.

We claim:

1. A water-insoluble monoazo dyestuff of the formula alkylene-Xi in which alkylene has at most 2 carbon atoms, A represents thiazolyl or thiazolyl substituted by nitro, cyano,

methyl, or phenyl groups, benzthiazolyl or benzthiazolyl substituted by chlorine, cyano, lower alkoxy or nitro groups, thiadiazolyl or a group of the formula Y represents hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, phenoxy, nitro, cyano, lower carbalkoxy or lower alkylsulphonyl, Z represents hydrogen, chlorine, bromine, lower alkyl, cyano or trifluoromethyl, Y, represents hydrogen, chlorine, bromine, lower alkyl, lower alkoxy, phenoxy or lower alkanoylamino, Z, represents hydrogen, lower alkyl or lower alkoxy, X, represents hydrogen, lower alkoxy, cyanoethoxy or phenyl, and X is 0 -0i-Ra in which R., is phenyl or phenyl substituted by chlorine, lower alkyl or lower alkoxy.

2. A water-insoluble monoazo dyestuff according to claim 1 of the formula I alkylene-X OzN N=N N alkylene-X1 Z Y1 in which alkylene has at most two carbon atoms, Y represents hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy, nitro, cyano, lower carbalkoxy or lower alkylsulphonyl, Z represents hydrogen, chloro, bromo, lower alkyl, cyano or" trifluoromethyl, Y, represents hydrogen, chloro, bromo, lower alkyl, lower alkoxy, phenoxy or lower alkanoylamino, Z, represents hydrogen, lower alkyl or lower alkoxy, X, represents hydrogen, lower alkoxy, cyanoethoxy, phenyl, and X is in which R is phenyl or phenyl substituted by chlorine,

lower alkyl, or lower alkoxy.

3. A dyestuff according to claim 1 in which X, is phenyl, lower alkyl or cyanoethoxy.

4. A dyestuff according to claim 3 in which R, is phenyl.

5. A dyestuff according to claim 4 in which X, is phenyl.

6. A dyestuff according to claim 4 in which X, is lower alkoxy.

7. A dyestuff according to claim 4 in which X, is cyanoethoxy. 

2. A water-insoluble monoazo dyestuff acCording to claim 1 of the formula
 3. A dyestuff according to claim 1 in which X1 is phenyl, lower alkyl or cyanoethoxy.
 4. A dyestuff according to claim 3 in which R4 is phenyl.
 5. A dyestuff according to claim 4 in which X1 is phenyl.
 6. A dyestuff according to claim 4 in which X1 is lower alkoxy.
 7. A dyestuff according to claim 4 in which X1 is cyanoethoxy. 